Production of diesterified phosphono derivatives of ketones



Patented Nov. 4, C 1952 PRODUCTION OF DIESTERIFIED PHOS- PHONO DERIVATIVES OF KETONES Franklin Johnston, St. Albans, W. Va., assignor, by mesne assignments, to Union Carbide and Carbon Corporation, a corporation of New York 7 No Drawing. Application March 5, 1949,

Serial No. 79,913

This invention relates to the production of a novel class'of aliphatic, aromatic and mixed aromatic-aliphatio ketones containing at least one diesterified phosphono group in the molecule; and more especially it concerns products of the reaction of an organic phosphite diester with an unsaturatedaliphatic, aromatic or mixed aliphatic-aromatic ketone containing at least one carbon-to-carbon double bond. Those unsaturated ketones containing only carbon and hydrogen in the molecule in addition to the carbonyl oxygen andthose wherein the double bond of a carbonyl carbon atom or atoms is conjugated with a carbon-to-carbon double bond in the molecule are particularly useful in the process.

The novel compounds of the invention are substituted alkanones which are free from olefinic and acetylenic unsaturation and which contain only carbon, hydrogen, oxygen and phosphorus in the molecular structure.

The compounds have potential utility for many purposes such as for starting materials for the production of other phosphorus-containing compounds, and as possible plasticizers for various synthetic resins including the polyvinyl halides and the resinous copolymers of vinyl chloride and vinyl acetate.

Most of the preferred novel compounds of the invention may be represented by the formula wherein R, R and R respectively, are selected from the class consisting of hydrogen and the alkyl, aralkyl and aryl groups, R is selected from the class consisting of the alkyl, aryl, benzyl, and RR'CXCI-IR groups wherein R, R and R are selected from the "aforesaid class; and X designates a diesterified phosphono radical-having the formula (R O)z wherein R represents a radical selected from the class of alkyl, aryl, 'aralkyl, cycloalkyl, alkoxyalkyl, aryloxyalkyl and cycloalkoxyalkyl radicals. Among the novel cycloaliphatic compounds of the invention are those having the general struc- 'ture:

CR5R6 CHR - wherein R, R, and X have the meanings indicated supra, and R. to R have the same mean- 1 10 Claims. (Cl. 260-461) ing as R. The preferred cycloaliphatic compounds are those wherein R and B to R respectively, can be hydrogen or an alkyl radical having one to four carbon atoms.

, Compounds of this new type may be produced in accordance with the invention by reacting the appropriate phosphite diester with an aliphatic, aromatic or mixed ketone containing at least one carbon-to-carbon double bond, and preferably those containing only carbon and hydrogen in addition to the carbonyl oxygen and those in which the carbonyl double bond is conjugated with another carbon-to-carbon double bond.

The reaction preferably is conducted with dry but not necessarily anhydrous reagents, and usually in the presence of a small amount, i. e., around 0.5% to 5%, of a condensation catalyst. However, theuse of a catalyst is not critical. The best results are secured with the alkaline condensation catalysts, among which are the alkali metals such as metallic sodium, potassium and lithium; alkali metal amides such as sodamide; alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal alkoxides such as sodium methylate and ethylate; and the secondary and tertiary amines.

Effective catalysts are the alkali metal and alkaline earth metal salts of phosphite diesters of the type (R O);l| M

wherein M is an alkali metal or alkaline earth metal atom, and R has the meaning hereinbefore designated.

In one preferred form of the invention the unsaturated ketone is added in successive increments to an agitated solution or dispersion of the phite diester solution for each mol of the diester present therein. When one mol of a diolefinic ketone is reacted with one mol of the phosphite diester a diesterified phosphono keto-der-ivative is made which contains an olefinic bond; but when two mols of a phosphite diester are reacted with one mol of a diolefinic ketone the resultant keto-derivative is free from olefinic and acetylenic bonds and contains two diesterified phosphono groups in the molecule. The resultant reaction mixture is neutralized or slightly acidified with a suitable mineral acid such as sulfuric, hydrochloric of phosphoric acid, or with an organic acid suchas-acetic acid. Glacial acetic acid isusually preferred for this purpose. The neutralized reaction mixture then may be washed with water to remove water-soluble materials and afterwards fractionally distilled undervacz-l.

uum, the fraction containing the diest'erified ph'osphono ketone being separately recovered:- It frequently is convenient to-di'lute the reaction: mixture with an inert volatile solvent for there action product before washing the latterwith. water to avoidemulsificationto adjust the gray-l ity of the organic liquid and to permit layering out of the water. The solvent then is removed during the subsequent f r'actional distillation.

'-The"condensation reaction maybe conducted in the presence of an inert volatile solvent. -.for the reactants. The usepf'suchasolvent is -not essential; but is desirable when the ketonastarting material is a solid under the' reactionconditio'ns, of is apo'or-solvent for the phosphite diester or for the catalyst'. -Suita'ble solvents 'in-. cl'ude' the" aliphatic" and aromatic hydrocarbons such as' n heptane; benzene and xylene; and

. phosphite and ethylidene acetone to produce 4- dibutylphesphono pentanone-2:

cargo o i u CHaCH=CHCOCHa oiago P-cnctnoocii, C4H9O a) CH:

ethers as diethyl'arid'dibutyl ethers, the di ethersbf the glycols 'ar'id 'dioxane. I Among the phosphi't'e diesters. useful: in. he process may be nientioned the methyl, 1: ethyl,

methox'yet'hyl, fl-e'thoxyethyl, 1 p butoxyethyl -and e phe'noxyethyl"phospliitediesters. f' The allzyl and 'aryl" phosphite diest'ers may. be produced by various procedures i known: ini the art. For" example, "certain of these=diesters can as the'vin'yl alkyl and vinyl arylketonese. g.-'-'-vinyl ethyl-ketone; vinyl -propyl 'ketone, 'vinylisopropyl ketone, vinyl 'isobutyl ketone; and vinyl phenyl ketone; alkenyl alkyl and alkenyl aryl ketones' such'as propenyl methyl ketone '(e'thy 1idene acetone) pro-penyl ethyl ketone 'prfopenyl' butyl ketone, propenyl phenyl ket'one, and I-biAtenyl ethyl ketone alkylidene 'acetones su'ch'as isopro'pylidene acetone '(mesityl oxide),

"isobiitylidene acetoneancl isohexylidene acetone;

1 unsaturated ketones useful in the substituted benzylidene aceton'essuch as 2=phenylpropenyl methyl'ketonei'and z-ben'zylpropenyl methyl ketone; benzylidenemethyl ethyl ketone benzylideneacetophenone; dypnone; and diolefinic ketones such as diisopropylideneacetone The following examples serve to illustrate the invention. In the examples all parts are given in terms of weight unless otherwise indicated.

,rTo a mixture of 1 94.parts (one mol), oidibutyl phosphite and l0gparts Qt sodamide in awessel provided: with an; a itator and reflux .condenser 84 7 parts (one. .mol) ofethylidene-acetone were added during 15 minutes,.-a nd the;iea9tiqn,.mix turewas cooled to maintain ,the temperature-near but below. 75,- ,C. The reaction was. complete in 5 minutes, and the reaction.mixture wasneutral ized with-glacialqacetic a. c ig i,. washed with.;.45.0 parts of water; and. fractionally. distilled under vacuum. y d n eaib t lphesmo o. an mo e- 2;as alight-amber liquid boilingrat 203$ C under aspressureof 2.3-;mr not, mercury, and having a refractive index of 1,45 03 at 30 C., and a specific gravity at 20 C. of 1.0630.

, v Example? zThree. parts .of metallic potassium, were. added to 125 ,parts '(;.51. mol) of .dicyclohexyl .phosphite with-heatingto 80,?- C. to complete the reaction with formation-otthe potassium, saltpi dicyclohexyl phosphite. ;-'1o-th is.-solutionfiS parts (.51 mol) of benzalacetone were rapidly-addeda itationof' e' xi ll i andth ilat r heated forjBQrminutesat t2 t omplete( h -reac After cooling the. mixturejo. 5.0.5. ,0. it was neutralized with glacial acetic acid, diluted with parts of-dibutyl ether, and ;washed,wil h 300 parts :of' water; The washed mixture was, ,filteredand the filtrate was: stripped of volatile .materials in a Claisentype still. to .a-.kettle;.=temperature of 1-75-C."at a pressure of 5.5 mm. or"v mercury. The residual product, .4ephenyl-4(dicyclohexylphosphono)butanone-2, was an oily red liquid having Erdi'iii le 3 During 15 minutes 146parts (one mol) of benzalacetone were added to an agitated solution of ,5" parts of sodamidefln; 194 parts (one mollof dibutyl pho-sphite-and the reaction continued for 20 minutes while adding 16 parts of -sodamide and maintaining the temperature at 58 (1-65 C. to complete the reaction. The mixture then was cooled to 30 C., neutralized with glacial acetic acid, diluted with; 250 cc. of benzene, and the benzene solution washed with 500 cc. of water. The benzene solution was filtered and the filtrate fractionallydistilled in a Claisen type still; and 4-,p heny1;4 (dibutylphosphonolbutanone-2 was separately recovered in 66% yield as an oily yellow liquid boiling at 192 C. under a pressure of 2.4 mm. of mercury, and having a specific gravity at C. of 1.0545 and a refractive index at 205 C. of 1.4898.

Example 4 To a solution of 5 parts of sodamide in 87 parts (0.45 mol) of dibutyl phosphite there were slowly added 104 parts (0.5 mol) of benzalacetophenone dissolved in 200 cc. of benzene, and 8 additional parts of sodamide then were added during 12 minutes While cooling to maintain the temperature near but below 70 C. The reaction mixture was cooled to C., neutralized with glacial acetic acid, diluted with 65 cc. of benzene, and washed with 500 cc, of water. The washed solution was filtered, and the filtrate was distilled to a kettle temperature of 151 C. under a pressure' of 2 mm. of mercury. The residue then was fractionally distilled under high vacuum,

yielding 2 phenyl 2 (dibutylphosphono) ethyl H temperature. After completion of the reaction forming the sodium salt of dibutyl phosphite, 208

parts (one mol) of benzalacetophenone dissolved 5 in 750 cc. benzene were added dropwise to the agitated solution during minutes. The mixture was heated to 85 C. for an additional hour to complete the reaction and then was neutralized with glacial acetic acid, diluted with 100 cc. of benzene, washed with 675 cc. of water, and the benzene solution stripped in a Claisen type still to a kettle temperature of 236 C. at 5 mm.

of mercury pressure. The resultant product, 2- phenyl-2- (diethylphosphono) ethyl phenyl ketone, was an amber, viscous liquid with a refractive index of 1.5767 at 30 C.

Example 6 222 parts (one mol) of dypnone (l-methylbenzylidenemethyl phenyl ketone) were mixed with 194 parts (one mol) of dibutyl phosphite and heated in an oven at 100 C. for 713 hours. The reaction mixture was stripped under vacuum in a Claisen type still to a kettle temperature of 218 C. under a pressure of 3.7 mm. of mercury,

thereby providing as residual product a yield of about 19% of 2-phenyl-2-dibutylphosphonopropyl phenyl ketone in the form of a dark viscous liquid. Upon distillation of this product in a molecular type high vacuum still the purified product was a reddish amber liquid boiling at 149 C. under a pressure of 4 microns of mercury. It had a specific gravity at 20 C. of 1.1048 and a refractive index at 30 C. of 1.5572.

Example 7 222 parts (one mol) of dypnone (l-methylbenzylidenemethyl phenyl ketone) were slowly added to and reacted with an agitated solution of 5.}parts of sodamide in 194 parts (one mol) of mixture filtered, and the filtrate fractionally distilled in a pot type still to a kettle temperature of 150 C. at 2.5 mm. of mercury pressure. The residue was fractionally distilled on a falling film type still, providing a yield of 59% of 2-phenyl-2- dibutylphosphonopropyl phenyl ketone.

This compound was compatible with a vinyl chloride-vinyl acetate copolymer resin containing around 95% of the chloride in the polymer in the respective proportions by weight of 1:2 or more.

Example 8 ,filtrate fractionally distilled under vacuum in a dibutyl phosphite during 1.5 hours while main- Claisen type still, providing a 47% yield of 4- methyl-4-(dibutylphosphono)pentanone 2 as a light yellow oily liquid having a boiling point of 158 C. under a pressure of 2.8 mm. of mercury, a specific gravity at 20 C. of 0.9967 and a refractive index at 30 C. of 1.4402.

Example 9 138 parts (one mol) of phorone were rapidly mixed with a solution of 10 parts of sodamide in 388 parts (2 mols) of dibutyl phosphite. Three additional parts of sodamide were introduced and the reaction completed at a maximum temperature of 44 C. The reaction mixture was neu- Example 10 138 parts (one mol) of isophorone were added dropwise to a solution of 12 parts of sodamide in 194 parts (one mol) of dibutyl phosphite. The temperature was kept below 70 C. by cooling. Then 6 parts of sodamide were added and the reaction was completed. The reaction mixture was neutralized with glacial acetic acid, diluted with 250 cc. of benzene, the mixture washed with 500 cc. of water, and the washed mixture filtered. The filtrate was fractionally distilled under vacuum in a Claisen type still, providing a 61% yield of 3,5,5 trimethyl S-(dibutylphosphono) cyclohexanone-l boiling at C. under a pressure of 2.2 mm. of mercury, and having a specific I gravity at 20 C. of 1.0180, and a refractive index at'30 C. of 1.4590.

In similar manner, in accordance with the invention, the reaction of diethyl phosphite and vinyl propyl ketone yields S-(diethylphosphono) hexanone-l; that of dimethoxyethyl phosphite and propenyl ethyl ketone yields S-(dimethoxyethylphosphono)hexanone-3; that of diphenoxyethyl phosphite and isopropylidene acetone yields 4 methyl-4-(diphenoxyethylphosphono)pentanone-2; that of dibenzyl phosphite and isobutylidene acetone yields 5-methyl-4-(dibenzylphosandfisobutenyl propyl ketone-yields' 6-rnethyl-6- (dioctylphosphono) heptanonelg and that ofdi-.

cyclohexyl.:zph osphit. and yin l ethyl ketone yields (dicyclohexylphosphono)pentanone 3. .=:I n;'the: accompanying, claims the ..term 1 diesterified phosphono-radicalfiiis intended to designate radicals of the formula wherein R hasthe-aforesaid meaning..- The term functional carbon. atom is intended to designate the carbonyl carbon atom of a keta group.

Iclaimr... i H ,t. 1.; Process tiorhpro ducing ketones having at least one diesterified phosphono radical attached to ,acorresponding carbon atombeta to a keto carbon atom; which. comprises reacting a phosphite-diester with an unsaturated ketone at a temperature-of f-rorn 0 C to 200 C. in the presence of a condensation-catalyst; the said ketone having at least one olefinio double bond, the double bond of the carbonyl carbon atom of a keto groupxloeingconjugatedwith a carbon-tocarbon doublejaondinsaid ketone, :;.=.2; Process;ifor; producing ketones having at least one .diesterified phosphono radical attached to:-a.;.corresponding carbon :atombeta to a keto carbom-atom, which; comprises reacting a phosphiteradiester withgan-unsaturated ketone at a temperature Of- IEIOIXI Q"; C.;to 200 C. in the pres- .ence of:an alkaline condensation catalyst, the said ketone having at least: one olefinic double vbond, the double bond of the carbonyl carbon atom ofga keto-group being conjugated with a carbon-to-carbon double bond in-said ketone.

.esBrocessi-for producing lietones having at least one diesterified phosphono radical attached to a corresponding carbon atom beta to a keto carbon atom, which comprises reacting a phosphite idiested with an unsaturated ketone at a temperature ,offrom 0 C; to 200 C. in the pres- .ence oLan alkaline condensation catalyst and oi tanhinert solvent for the reactants, said ketone shaving atleast one olefinic-double bond, the dou- .ble.bond.-of the carbonyl carbon atom of a keto .group being conjugated with a carbon-to-carbon double .bond in said ketoneh a d Process ,for producing ketones having at least onediesterified phosphono radical attached .to'a corresponding carbon atom beta to a keto carbon atom, which comprises reacting at a temperatureof from 0 C. to 200 C., in the presence of acondensation catalyst, a phosphite diester and. an, unsaturated ketone having from one to two-olefinic double bonds and havinga structure corresponding to the formula RCRX=CR COR wherein R, is selected from th class consisting of hydrogen and the alkyl, aralkyl, aryl and masts arallienyl radicals Rv and R? areselected from the class consistingiof hydrogen and'the alkyl; aralkyl and aryl radicals; and R is' selected from the group consisting, of the alkyl, phenyl, benzyl and .CR?= CR{R radicals wherein R, R and RFare selected. from the aforesaid classes.

;5 Pr o cess for producing .ketones having at least one diesterifiedphosphono radical attached to acorresponding.carbon atom beta to a keto carbonatozn, which comprisesreactin'g a phosphite' ,diester with an unsaturated ketoneji at a temperature offromi0 C. to 200? C the said least one.o1'efinic, double bond, the doub e bond of the carbonyl carbon atom of a l eto group being conjugated with a' carbon-tocarbon double bondin said'lietone, a 6. As new compounds; lketo'ne' free from olefinic and acetylenic unsaturation, said ketones having two. diesterified phosphono'vradicals attachedto corresponding carbon atoms respectively. beta to a keto carbon atom.

ketone having at astrucam o oniv H p h 0 I wherein R Bflandfi to R respectively, designateradicalsselected from the class consisting of hydrogen and the alkyl, ar'alkyl and aryl radicals; and X designates a diesterified phosphono radical having the formula v (R4O)2P wherein R4 r pre ents a radical'selec'ted from the class consisting of the alkyl, aryl, 'aralkyl, cycloalkyl alkoxyalkyl, aryloxalkyl and cycloalkoxyalkyl radicals. i v [10. As a new compound, 3,"5,'5-trim'ethyl 34dibutylphosphono)cyclohexanone l.

FRANKLIN JOHNSTON.

REF citations can) The followingreferences areo f record in the file of this patent:

n UNITED. STATES PA'rEN T's Number 

1. PROCESS FOR PRODUCING KETONES HAVING AT LEAST ONE DIESTERIFIED PHOSPHONO RADICAL ATTACHED TO A CORRESPONDING CARBON ATOM BETA TO KETO CARBON ATOM, WHICH COMPRISES REACTING A PHOSPHITE DIESTER WITH AN UNSATURATED KETONE AT TEMPERATURE OF FROM 0* C. TO 200* C. IN THE PRESENCE OF A CONDENSATION CATALYST, THE SAID KETONE HAVING AT LEAST ONE OLEFINIC DOUBLE BOND, THE DOUBLE BOND OF THE CARBONYL CARBON ATOM OF A KETO GROUP BEING CONJUGATED WITH A CARBON-TOCARBON DOUBLE BOND IN SAID KETONE.
 6. AS NEW COMPOUNDS, KETONES FREE FROM OLEFINIC AND ACETYLENIC UNSATURATION, SAID KETONES HAVING TWO DIESTERIFED PHOSPHONO RADICALS ATTACHED TO CORRESPONDING CARBON ATOMS RESPECTTIVELY BETA TO A KETO CARBON ATOM. 